Polishing agent for synthetic quartz glass substrate

ABSTRACT

Disclosed is a polishing agent for synthetic quartz glass substrates, which is characterized by containing a colloidal solution of a colloidal silica or the like having a colloid concentration of 20-50% by mass, and a polycarboxylic acid polymer, an acidic amino acid, a phenol or a glycosaminoglycan.

TECHNICAL FIELD

This invention relates to a polishing slurry for use with syntheticquartz glass substrates for main use in semiconductor-related electronicmaterials, nano-imprint-related materials, and display-relatedmaterials, especially synthetic quartz glass substrates for use in theadvanced semiconductor-related electronic materials and liquidcrystal-related materials.

BACKGROUND ART

Qualities of synthetic quartz glass substrates include the size anddensity of defects on substrates, flatness, surface roughness,photochemical stability of material, and surface chemical stability. Ofthese, the quality relating to defects on substrates encountersincreasingly rigorous requirements in accordance with the trend of ICtechnology toward finer feature size processing and of display panelstoward larger size.

While improvements in the defective quality of synthetic quartz glasssubstrates have been continuously made, the substrates used so far inthe semiconductor technology, for example, are those substrates whererecessed defects with a size of less than about 0.3 μm are substantiallypresent. This is especially because a detection probability of defectswith a size of up to 0.5 μm is low upon visual inspection under acollective lamp at an illuminance level causing no hygienic issue, ordefect inspection by an automatic defect inspector as described in JP-AS63-200043 (Patent Document 1) and JP-A S63-208746 (Patent Document 2).This leads to a delay in the substrate quality improving approach.

Under the background, a high-sensitivity defect inspector was recentlydeveloped. Research works have progressed for controlling microscopicsurface defects using this inspector. While JP-A S64-40267 (PatentDocument 3) describes a process of polishing a glass substrate withcolloidal silica to produce a precise mirror finish surface, this wasfound unsatisfactory as the microscopic defect controlling processbecause an analysis of surface defects by said high-sensitivity defectinspector demonstrated the presence of microscopic raised/recesseddefects. In JP-A 2002-030274 (Patent Document 4), colloidal silica isdescribed as the polishing slurry for aluminum disks and glass harddisks. It is described that the preferred SiO₂ concentration is in arange of 1 to 30% by mass, and Examples carry out polishing with apolishing slurry having a SiO₂ concentration of 10% or 14% by mass.

However, when synthetic quartz glass substrates are polished in theabove-described concentration range, numerous defects with a size of upto 0.5 μm are generated. Likewise in JP 2987171 (Patent Document 5) andJP-A 2001-003036 (Patent Document 6) relating to a colloidalsilica-based polishing slurry as the polishing slurry for siliconwafers, substantially the colloidal silica-based polishing slurry isdiluted to a SiO₂ concentration of up to 10% by mass prior to use. It isthen undesirable as the polishing slurry for photomask-forming glasssubstrates.

JP-A 2004-98278 describes that microscopic raised defects can beeliminated using high purity colloidal silica near neutrality. In fact,it is impossible to use such colloidal silica in the neutral range in aconsistent manner because even those high purity products having minimalcontents of metals and other impurities tend to gel or thicken or changethe particle size distribution of abrasive grains with iteration ofpolishing.

Accordingly, such a process has a serious issue that recycling of thepolishing slurry for repeated use is difficult, and inevitably thepolishing slurry has to be utilized as a one-way stream, which isunfavorable in economical and environmental aspects.

Also, in the case of liquid crystal substrates, for example, furtherdefect control is desired because photomask-forming synthetic quartzglass substrates of larger size are used as the size of liquid crystalpanels increases.

SUMMARY OF INVENTION Problem to Be Solved by Invention

An object of the invention, which has been made under the circumstances,is to provide a polishing slurry for synthetic quartz glass substrates,capable of controlling the formation of defects and increasing the yieldof manufacture of semiconductor devices, display panels or the like.

Means for Solving Problem

Making extensive investigations to attain the above object, theinventors have found that a polishing slurry comprising a colloidalsolution such as colloidal silica and a carboxylic acid polymer, anacidic amino acid, a phenol or a glycosaminoglycan is effective forovercoming the above-discussed problems. The invention is predicated onthis finding.

Specifically, the invention provides a polishing slurry for use withsynthetic quartz glass substrates, as defined below.

(1) A polishing slurry for synthetic quartz glass substrates, comprisinga colloidal solution and a component selected from the group consistingof a carboxylic acid polymer, an acidic amino acid, a phenol, and aglycosaminoglycan, said colloidal solution having a colloidconcentration of 20 to 50% by mass.

(2) The polishing slurry for synthetic quartz glass substrates of (1)wherein the colloidal solution is a colloidal silica dispersion.

(3) The polishing slurry for synthetic quartz glass substrates of (1) or(2) wherein the carboxylic acid polymer is an acrylic acid polymer.

(4) The polishing slurry for synthetic quartz glass substrates of (1) or(2) wherein the acidic amino acid is aspartic acid or glutamic acid.

(5) The polishing slurry for synthetic quartz glass substrates of (1) or(2) wherein the phenol is catechol, resorcinol or hydroquinone.

(6) The polishing slurry for synthetic quartz glass substrates of (1) or(2) wherein the glycosaminoglycan is hyaluronic acid.

(7) The polishing slurry for synthetic quartz glass substrates of anyone of (1) to (6), having pH 9 to 10.5.

(8) The polishing slurry for synthetic quartz glass substrates of (7)wherein the pH is adjusted with one or more selected from the groupconsisting of an alkali metal hydroxide, alkaline earth metal hydroxide,basic salt, amine, and ammonia.

(9) The polishing slurry for synthetic quartz glass substrates of anyone of (1) to (8) wherein the synthetic quartz glass substrate is aphotomask-forming synthetic quartz substrate.

Advantageous Effects of Invention

In the manufacture of synthetic quartz glass such as synthetic quartzglass substrates for forming photomasks to be used in thephotolithography that is important in the manufacture of IC or the like,according to the invention, the formation of defects on the surface ofsynthetic quartz glass substrates which are detectable by thehigh-sensitivity defect inspector is inhibited, an increase in the yieldof manufacture of semiconductor devices or the like is expectable, and afurther reduction of feature size in the semiconductor industry isachievable.

Also, for photomask-forming synthetic quartz glass substrates with endfaces having a certain thickness used in display-related materials, theinvention inhibits the formation of defects during polishing andimproves the yield of manufacture.

DESCRIPTION OF EMBODIMENTS

The polishing slurry for synthetic quartz glass substrates according tothe invention comprises a colloidal solution and one or more componentsselected from among carboxylic acid polymers, acidic amino acids,phenols, and glycosaminoglycans.

The colloidal solution used herein preferably contains colloidalparticles of a fine particle size, and specifically a primary particlesize of preferably 5 to 500 nm, more preferably 10 to 200 nm, and mostpreferably 20 to 150 nm. With too small a particle size, colloidalparticles tend to attach or adhere to the substrate surface, interferingwith cleaning. Particles with too large a particle size may permit asubstrate as polished to have a poor surface roughness and beundesirable as the polishing slurry for final precision polishing. It isnoted that the particle size is a measurement by the dynamic lightscattering method.

The colloidal solution has a concentration of 20 to 50% by mass, andpreferably 35 to 45% by mass. With a concentration of less than 20% bymass, microscopic flaws are formed on the glass surface. With aconcentration of more than 50% by mass, the polishing slurry becomesunstable and increases its viscosity to inhibit polishing.

The particle size distribution may be either monodisperse orpolydisperse or have a plurality of particle size peaks.

Types of colloidal particles include colloidal silica, colloidal ceria,and colloidal zirconia, with colloidal silica being most preferred.

With respect to the particle shape, colloidal silicas dispersed invarious colloidal forms including spherical, cocoon, and coupled formsare available, with the colloidal silica in spherical form beingpreferred.

Colloidal silicas include those from various preparation methods, forexample, those granulated from water glass, and those obtained fromhydrolysis of organic silicate compounds such as alkoxysilanes. Manydispersing media generally have alkaline pH from the standpoint ofstorage stability although neutral or acidic pH may be acceptable.Preferred are pH values in the range of 3 to 5 or in the range of 8 to11. More preferred are pH values in the range of 9 to 10.5. At pH nearneutrality, the polishing slurry may tend to be unstable. At too strongalkalinity, surface roughness may occur on the glass as polished.

Further, while silica abrasive grains are generally used as dispersed inwater, they may also be dispersed in an organic solvent such asmethanol, isopropanol, ethylene glycol, methyl ethyl ketone, toluene, orxylene or a mixture thereof. Moreover, of these organic solvents andmixtures thereof, water-soluble ones may be mixed with water in anydesired proportion.

As the colloidal silica dispersion liquid, commercially availableproducts may be used, for example, COMPOL-50, COMPOL-80, COMPOL-120 andCOMPOL-EX111 from Fujimi Inc., ST-XL, ST-YL, and ST-ZL from NissanChemical Industries, Ltd., SYTON from Dupont, NALCO series from NittaHaas Inc., and GP series from Fuso Chemical Co., Ltd.

When the dispersion or polishing slurry is used to polish glasssubstrates, one or multiple components selected from among carboxylicacid polymers, acidic amino acids, phenols, and glycosaminoglycans areadded to the polishing slurry, thereby reducing the number of defectswhich are detectable by the high-sensitivity defect inspector.

The inventors made investigations on the defect forming mechanism basedon the following hypothesis.

With respect to abrasive grains in the polishing slurry, condensationoccurs between grain surfaces due to the work by polishing action, orcondensation occurs between glass swarf removed from the surface beingpolished and abrasive grains, to create active particles which can causedefects, which then condense or attach to the surface, end face orchamfered edge under the polishing action, or form flaws on the surface.It is thus recognized that the stability of abrasive grains in thepolishing slurry is important.

Also, since end faces or chamfered edges of a synthetic quartz glasssubstrate for a large-size photomask for use in the display applicationhave not been mirror finished as opposed to the front and rear surfacesthereof, the tendency that the polishing slurry adheres thereto as drydeposits during the polishing operation becomes stronger as thesubstrate becomes thicker.

In general, for substrate polishing, either double-side or single-sidepolishing may be employed. The time required for the polishing of alarge-size synthetic quartz glass substrate is at least several tens ofminutes, and sometimes ten or more hours. While the surface to bepolished is always kept in contact with the polishing slurry and thuswetted, the end face and chamfered edge in the case of double-sidepolishing or the end face, chamfered edge and rear surface in the caseof single-side polishing become surfaces not subject to polishing whereadhesion and drying of the polishing slurry continue intermittently overa long time. As adhesion of the polishing slurry continues for a longtime on the front and rear surfaces being polished and intermittentadhesion and drying of the polishing slurry occur on those surfaces notsubject to polishing, solid deposits form which are not readily scrapedoff. Such solid deposits are not completely removed during the cleaningstep following polishing, and if spalled off, they cause surfacedefects, or if carried from the end face to the front surface duringcleaning, they become dry stains (or flow stains). These phenomena arisefrom the specialty of polishing of large-size synthetic quartz glasssubstrates because they are not regarded problematic with conventionalsemiconductor-related substrates wherein the polishing time is generallyas short as several tens of minutes, and about one hour at the longest,and the substrate is always kept wet in contact with the polishingslurry during the polishing step. It is then recognized that on thesurface not subject to polishing, the ease of removal of the polishingslurry after condensation or dry attachment is also important.

In the polishing method using high purity colloidal silica in theneutral region as described in the above-referred JP-A 2004-98278, forexample, the adhesion of grains on the glass surface in chemicalreaction mode may be restrained because of a weak electric repulsiveforce between grains due to a low zeta-potential on grain surfaces ascompared with alkaline colloidal silica in the stable region around pH10. However, since abrasive grains condense together due to mechanicalaction of polishing, a sudden gelation or viscosity buildup is observed.Thus the method cannot be used in practice. Even when the polishingpressure is moderated so as to minimize instability, the particle sizedistribution is shifted to a higher size by the work of shear forces ofthe polishing plate, causing flaws on the surface.

In the above situation, when a carboxylic acid polymer is added to thepolishing slurry, a protective colloid action may be induced or abrasivegrains be taken in the network structure of polymeric sol-gel. It isthen possible to inhibit mutual approach and condensation of abrasivegrains in the polishing slurry and also to inhibit particles formed bycondensation of abrasive grains from condensing or adhering to theas-polished glass substrate surface or colliding against the surface toform flaws.

Preferred types of the carboxylic acid polymer include acrylic acidpolymers, maleic acid polymers, and phthalic acid polymers. Theconcentration of carboxylic acid polymer is preferably 0.001 to 1.0% bymass, and more preferably 0.01 to 0.5% by mass based on the solids inthe colloidal solution, specifically the mass of silica. Too low aconcentration may fail to achieve an effect sufficient to inhibit flawswhereas too high a concentration may obstruct a stable supply of thepolishing slurry to the polisher because of a high viscosity of the highmolecular polymer. The carboxylic acid polymer preferably has a weightaverage molecular weight of 1,000 to 100,000,000, and more preferably10,000 to 10,000,000. Too low a molecular weight may fail to achieve aneffect sufficient to inhibit flaws whereas too high a molecular weightmay obstruct a stable supply of the polishing slurry to the polisherbecause of a high viscosity.

It is noted that the weight average molecular weight is as measured bygel permeation chromatography (GPC) versus polystyrene standards.

Exemplary water-soluble polymers other than the carboxylic acid polymersinclude cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone,and polyacrylamide. These water-soluble polymers are expected to exertsome effects on the condensation and adhesion of grains and theformation of flaws. Nevertheless, the carboxylic acid polymers are mosteffective because negatively charged carboxyl ions are repulsive to eachother to facilitate spreading of the network so that abrasive grains maybe effectively taken therein, and are also repulsive to the glasssubstrate surface which is a negatively charged object to be polished.

Of the abrasive grains which are readily taken in the network,electrically charged colloidal particles are preferred. The size of theabrasive grains which are readily taken in the network is preferably 5to 500 nm, more preferably 10 to 200 nm, and most preferably 20 to 150nm.

Also, when an acidic amino acid is added to the polishing slurry, theelectrical stability of the colloidal silica polishing slurry can beincreased. The acidic amino acid having a relatively low isoelectricpoint among amino acids has a greater negative surface charge in a basicsolution of higher pH and functions to inhibit mutual approach andcondensation of abrasive grains in the polishing slurry, and also toinhibit particles formed by condensation of abrasive grains fromcondensing or adhering to the as-polished glass substrate surface orcolliding against the surface to form flaws.

Preferred types of the acidic amino acid are aspartic acid and glutamicacid. The concentration of acidic amino acid is preferably 0.05 to 10.0%by mass, and more preferably 0.5 to 3.0% by mass based on the solids inthe colloidal solution, specifically the mass of silica. Too low aconcentration may fail to achieve an effect sufficient to inhibit flawswhereas too high a concentration may lead to a polishing slurry having ahigher ion concentration which is susceptible to salting-out of colloidand rather becomes unstable.

Exemplary amino acids other than the acidic amino acid includeasparagine, serine, threonine, lysine, etc. These amino acids areexpected to exert some effects on the condensation and adhesion ofgrains and the formation of flaws. Nevertheless, the acidic amino acidis most effective because the acidic amino acid is highly negativelycharged in a basic solution and is repulsive to the negatively chargedabrasive grains and glass substrate surface which is an object to bepolished.

It is also effective to add a phenol to the polishing slurry. It isknown that the phenol is present in the form of phenolate in an aqueoussolution as it dissociates into proton and phenolate. Negatively chargedphenolate can enhance the electrical stability of the colloidal silicapolishing slurry. Specifically, negatively charged phenolate functionsto inhibit mutual approach and condensation of abrasive grains in thepolishing slurry, and also to inhibit particles formed by condensationof abrasive grains from condensing or adhering to the as-polished glasssubstrate surface or colliding against the surface to form flaws.

Preferred types of the phenol include phenol, cresol, xylenol, naphthol,catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol and saltsthereof. Inter alia, catechol, resorcinol, and hydroquinone arepreferred from the standpoints of solubility in aqueous medium polishingslurry and electric charge. The concentration of the phenol ispreferably 0.05 to 10.0% by mass, and more preferably 0.5 to 3.0% bymass based on the solids in the colloidal solution, specifically themass of silica. Too low a concentration may fail to achieve an effectsufficient to inhibit flaws whereas at too high a concentration, thephenol may not be thoroughly dissolved.

Although alcohols such as methanol and ethanol are compounds similar tothe phenol, the alcohol which is not ionized in solution due to a lowacidity does not contribute to electrical stability as does the phenol.

Further, when a glycosaminoglycan is added to the polishing slurry, theelectrical stability of the colloidal silica polishing slurry can beincreased due to its physical property of strong negative charges andabrasive grains be taken in the network structure of polymeric sol-gel.It is then possible to inhibit mutual approach and condensation ofabrasive grains in the polishing slurry, and also to inhibit particlesformed by condensation of abrasive grains from condensing or adhering tothe as-polished glass substrate surface or colliding against the surfaceto form flaws.

Preferred types of the glycosaminoglycan include hyaluronic acid,heparan sulfate, chondroitin sulfate, keratan sulfate and salts thereof.The concentration of glycosaminoglycan is preferably 0.001 to 1.0% bymass, and more preferably 0.01 to 0.5% by mass based on the solids inthe colloidal solution, specifically the mass of silica. Too low aconcentration may fail to achieve an effect sufficient to inhibit flawswhereas too high a concentration may obstruct a stable supply of thepolishing slurry to the polisher because of a high viscosity ofglycosaminoglycan.

The glycosaminoglycan preferably has a weight average molecular weightof 1,000 to 100,000,000, and more preferably 10,000 to 10,000,000. Toolow a molecular weight may fail to achieve an effect sufficient toinhibit flaws whereas too high a molecular weight may obstruct a stablesupply of the polishing slurry to the polisher because of a highviscosity.

It is noted that the weight average molecular weight is as measured bygel permeation chromatography (GPC) versus polystyrene standards.

Exemplary water-soluble polymers other than the glycosaminoglycaninclude cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone,and polyacrylamide. These water-soluble polymers are expected to exertsome effects on the condensation and adhesion of grains and theformation of flaws. Nevertheless, the glycosaminoglycan is mosteffective because negatively charged carboxyl and sulfate groups arerepulsive to each other to facilitate spreading of the network so thatabrasive grains may be effectively taken therein, and are also repulsiveto the glass substrate surface which is a negatively charged object tobe polished. It is further expectable that the glycosaminoglycan has sostrong a water-retaining action that it may also be effective inpreventing drying and adhesion of the polishing slurry on the substratesurface when a glass substrate is taken out of the polisher after thecompletion of polishing.

It is noted that in addition to the above-illustrated additives, otheradditives such as pH modifiers, buffer agents and rust preventives maybe added. In particular, pH adjustment of the polishing slurry isimportant in controlling microscopic defects. It is thus desirable toadd a pH modifier in order to provide pH in the range of 9 to 10.5.

Suitable pH modifiers which can be used herein include alkali metalhydroxides, alkaline earth metal hydroxides, basic salts, amines, andammonia. Examples include potassium hydroxide, sodium hydroxide, calciumhydroxide, sodium borate, monoethanolamine, diethanolamine,triethanolamine, and ethylenediamine. The additives exemplified abovemay be used alone or in combination of two or more. Inter alia,diethanolamine or triethanolamine is preferred.

The pH modifier is preferably added in such an amount as to provide pHin the range of 9 to 10.5. Since it is important that the pH of thepolishing slurry does not deviate from this range during polishing, thesequence of adding other additives in advance and adding the pH modifierlater is preferred. If the pH of the polishing slurry varies duringpolishing, the pH modifier may be added at an appropriate point of timeso as to provide pH 9 to 10.5. In the case of strong bases having a highdissociation constant like alkali metal hydroxides, pH adjustment isdifficult because in the relevant pH range, even a small difference inaddition amount may result in a substantial variation of pH. In thisregard, diethanolamine and triethanolamine which are bases of moderatestrength are the preferred pH modifiers. At pH near neutrality,colloidal silica tends to be unstable which is inconvenient tocontinuous polishing. At too high pH, surface roughening may occur onthe as-polished quartz glass.

Additives other than the pH modifier which can be used herein includecarboxylic acids and salts thereof. Specifically, carboxylic acids ofchain structure having a molecular weight of at least 100 and aromaticcarboxylic acids are preferred. Examples include methacrylic acid,succinic acid, maleic acid, fumaric acid, tartaric acid, malic acid,adipic acid, citric acid, benzoic acid, methylbenzoic acid,t-butylbenzoic acid, salicylic acid, phthalic acid, isophthalic acid,terephthalic acid, phenylacetic acid, and salts thereof. The additivesexemplified above may be used alone or in combination of two or more.Since these molecules are water soluble and bulky, they have theadvantage that when added to the polishing slurry, the moleculescoordinate with colloidal particles to stabilize the colloidal state.

The synthetic quartz glass substrate to be polished herein is obtainedfrom a synthetic quartz glass ingot through steps of shaping, annealing,slicing, lapping and rough-polishing. This is followed by a precisionpolishing step dictating the final surface quality where the substrateis polished using the polishing slurry for synthetic quartz glasssubstrates of the invention.

It is noted that the polishing mode using the polishing slurry of theinvention is typically batchwise double-side polishing althoughsingle-side polishing and single-wafer polishing may also be acceptable.

The synthetic quartz glass substrate which is polished using thepolishing slurry of the invention may be used in the fields ofsemiconductor-related electronic materials and liquid crystals, andespecially as photomasks.

For example, semiconductor-related substrates are dimensioned 152 mm by152 mm by about 6.35 mm thick. In the case of nano-imprint substrates,since the nano-imprint technology is adapted to manufacture a smallnumber of many different products, substrates of various sizes may becontemplated, including those of 152 mm by 152 mm by about 6.35 mm thicklike the semiconductor substrates, those of 65 mm by 65 mm by about 6.35mm thick, and wafer substrates having a diameter of 150 mm and athickness of 0.5 to 1.0 mm.

On the other hand, in the case of liquid crystal-related materials,substrates include those of 330 mm by 450 mm by 5 mm thick, those of 800mm by 920 mm by 8 mm or 10 mm thick, those of 1220 mm by 1400 mm by 13mm thick, and those of 1600 to 1800 mm by 1700 to 1900 mm by 16 to 20 mmthick.

EXAMPLE

Examples and Comparative Examples are given below for illustrating theinvention, but the invention is not limited thereto. In Examples, theparticle size is as measured by the dynamic light scattering method.

Example 1

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped, after which rough-polishing and final precision polishing werecarried out by a double-side polisher. A soft suede-type polishing padwas used and a polishing slurry was used comprising a colloidal silicawater dispersion having a SiO₂ concentration of 40% by mass (FujimiInc., primary particle size 78 nm) to which 0.5% by mass of sodiumpolyacrylate (weight average molecular weight 250,000-700,000, Wako PureChemical Industries Ltd.) was added and diethanolamine was added toadjust to pH 10.0. Polishing was done under a load of 100 gf while thepolishing allowance was an amount sufficient to remove the flawsintroduced in the rough-polishing step (at least about 1 μm).

The polishing was followed by cleaning and drying, after which defectinspection was carried out using a laser conforcal optical systemhigh-sensitivity defect inspector (Lasertec Corp.). The number ofdefects with a size of at least 0.15 μm was 4.0 on the average.

Example 2

Defect inspection was done as in Example 1 except that sodiumpolymaleate (weight average molecular weight 1,000, Toa Gosei Co., Ltd.)was used instead of the sodium polyacrylate in Example 1. The number ofdefects was 7.1 on the average.

Example 3

Defect inspection was done as in Example 1 except that an acrylicacid/maleic acid copolymer (weight average molecular weight 60,000,Nippon Shokubai Co., Ltd.) was used instead of the sodium polyacrylatein Example 1. The number of defects was 4.4 on the average.

Example 4

Defect inspection was done as in Example 1 except that 0.5% by mass ofsodium polyacrylate (weight average molecular weight 20,000-700,000,Wako Pure Chemical Industries Ltd.) and 0.5% by mass of benzoic acidwere used instead of the sodium polyacrylate in Example 1. The number ofdefects was 3.2 on the average.

Example 5

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 0.5% by mass of sodiumpolyacrylate (weight average molecular weight 250,000-700,000, Wako PureChemical

Industries Ltd.) was added (the addition of sodium polyacrylate resultedin polishing slurry at pH 7.6). Polishing was done under a load of 100gf while the polishing allowance was an amount sufficient to remove theflaws introduced in the rough-polishing step (at least about 1 μm).

Defect inspection was done as in Example 1, finding that the number ofdefects was 4.3 on the average.

Example 6

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 0.5% by mass of sodiumpolyacrylate (weight average molecular weight 250,000-700,000, Wako PureChemical Industries Ltd.) was added and diethanolamine was added toadjust to pH 10.0. Polishing was done under a load of 100 gf while thepolishing allowance was an amount sufficient to remove the flawsintroduced in the rough-polishing step (at least about 1 μm).

Defect inspection was done as in Example 1, finding that the number ofdefects was 2.3 on the average.

Example 7

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 0.5% by mass of sodiumpolyacrylate (weight average molecular weight 250,000-700,000, Wako PureChemical Industries Ltd.) was added and diethanolamine was added toadjust to pH 10.0. Polishing was done under a load of 100 gf while thepolishing allowance was an amount sufficient to remove the flawsintroduced in the rough-polishing step (at least about 1 μm). Polishingwas continued just until the polishing pad was worn out.

Defect inspection was done as in Example 1, finding that the number ofdefects was 3.3 on the average for those substrates polished in theinitial stage and 3.5 on the average for those substrates polished inthe last stage.

Example 8

A silica synthetic quartz glass substrate stock as sliced (1220 mm×1400mm×13 mm thick) was lapped and rough-polished by a single-side polisher,after which it was subjected to final precision polishing by adouble-side polisher. At this point, the end face of the substrate had asurface roughness (Ra) of 0.2 μm.

A soft suede-type polishing pad was used and a polishing slurry was usedcomprising a high-purity colloidal silica water dispersion resultingfrom hydrolysis of alkoxysilanes and having original pH 7 and a SiO₂concentration of 40% by mass (Fuso Chemical Co., Ltd., primary particlesize 104 nm) to which 0.5% by mass of sodium polyacrylate (weightaverage molecular weight 250,000-700,000, Wako Pure Chemical IndustriesLtd.) was added and diethanolamine was added to adjust to pH 10.0.Polishing was done under a load of 70.0 gf for 4 hours while thepolishing allowance was an amount sufficient to remove the flawsintroduced in the rough-polishing step (at least about 3 μm).

The polishing was followed by cleaning and drying, after which defectinspection was carried out using a light scattering defect inspector(Lasertec Corp.). No stains flowing away from the end face wereobserved, and the number of defects with a size of at least 0.3 μm was0.5/100 cm² on the average.

Example 9

Defect inspection was done as in Example 8 except that sodiumpolymaleate (weight average molecular weight 1,000, Toa Gosei Co., Ltd.)was used instead of the sodium polyacrylate in Example 8. No stainsflowing away from the end face were observed, and the number of defectswith a size of at least 0.3 μm was 0.8/100 cm² on the average.

Example 10

Defect inspection was done as in Example 8 except that an acrylicacid/maleic acid copolymer (weight average molecular weight 60,000,Nippon Shokubai Co., Ltd.) was used instead of the sodium polyacrylatein Example 8. No stains flowing away from the end face were observed,and the number of defects with a size of at least 0.3 μm was 0.7/100 cm²on the average.

Example 11

Defect inspection was done as in Example 8 except that 0.5% by mass ofsodium polyacrylate (weight average molecular weight 20,000-700,000,Wako Pure Chemical Industries Ltd.) and 0.5% by mass of benzoic acidwere used instead of the sodium polyacrylate in Example 8. No stainsflowing away from the end face were observed, and the number of defectswith a size of at least 0.3 μm was 0.4/100 cm² on the average.

Example 12

A silica synthetic quartz glass substrate stock as sliced (1600 mm×1700mm×18 mm thick) was lapped and rough-polished, after which it wassubjected to final precision polishing. A soft suede-type polishing padwas used and a polishing slurry was used comprising a high-puritycolloidal silica water dispersion resulting from hydrolysis ofalkoxysilanes and having original pH 7 and a SiO₂ concentration of 40%by mass (Fuso Chemical Co., Ltd., primary particle size 104 nm) to which0.5% by mass of sodium polyacrylate (weight average molecular weight250,000-700,000, Wako Pure Chemical Industries Ltd.) was added (theaddition of sodium polyacrylate resulted in polishing slurry at pH 7.6).Polishing was done under a load of 70.0 gf while the polishing allowancewas an amount sufficient to remove the flaws introduced in therough-polishing step (at least about 3 μm).

On defect inspection as in Example 8, no stains flowing away from theend face were observed, and the number of defects with a size of atleast 0.3 μm was 0.5/100 cm² on the average.

Example 13

The procedure was the same as in Example 12 except that a polishingslurry was used comprising a high-purity colloidal silica waterdispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 0.5% by mass of sodiumpolyacrylate (weight average molecular weight 250,000-700,000, Wako PureChemical Industries Ltd.) was added and diethanolamine was added toadjust to pH 10.0, the polishing load was 70.0 gf, and the polishingallowance was an amount sufficient to remove the flaws introduced in therough-polishing step (at least about 3 μm).

On defect inspection as in Example 8, no stains flowing away from theend face were observed, and the number of defects with a size of atleast 0.3 μm was 0.5/100 cm² on the average.

Example 14

The procedure was the same as in Example 12 except that a polishingslurry was used comprising a high-purity colloidal silica waterdispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 0.5% by mass of sodiumpolyacrylate (weight average molecular weight 250,000-700,000, Wako PureChemical Industries Ltd.) was added and diethanolamine was added toadjust to pH 10.0. The polishing load was 70.0 gf, and the polishingallowance was an amount sufficient to remove the flaws introduced in therough-polishing step (at least about 3 μm). Polishing was continued justuntil the polishing pad was worn out.

On defect inspection as in Example 1, no stains flowing away from theend face were observed, and the number of defects was 0.5/100 cm² on theaverage for those substrates polished in the initial stage and 1.2/100cm² on the average for those substrates polished in the last stage.

Comparative Example 1

The procedure was the same as in Example 1 except that the sodiumpolyacrylate added to the polishing slurry used in the final polishingstep in Example 1 was omitted. Defect inspection was similarly carriedout using a laser conforcal optical system high-sensitivity defectinspector, finding that the number of defects was 52 on the average.

Comparative Example 2

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used, and apolishing slurry comprising a high-purity colloidal silica waterdispersion resulting from hydrolysis of alkoxysilanes and having pH 7and a SiO₂ concentration of 40% by mass (Fuso Chemical Co., Ltd.,primary particle size 104 nm) was used without addition of sodiumpolyacrylate. Polishing was done under a load of 100 gf while thepolishing allowance was an amount sufficient to remove the flawsintroduced in the rough-polishing step (at least about 1 μm).

As a result, the polishing slurry showed a viscosity buildup at thefourth batch from the start of polishing operation so that the polishingoperation became difficult, and the polishing operation becamesubstantially impossible at the sixth batch.

Defect inspection was carried out as in Example 1, finding that thenumber of defects was 10.9 on the average for those substrates polishedin the initial stage and 265 on the average for those substratespolished in the last stage (sixth batch).

Comparative Example 3

The procedure was the same as in Example 8 except that the sodiumpolyacrylate added to the polishing slurry used in the final polishingstep in Example 8 was omitted. Defect inspection was carried out using alight scattering defect inspector (Lasertec Ltd.). Stains flowing awayfrom the end face were observed, and the number of defects with a sizeof at least 0.3 μm was 50/100 cm² on the average.

Comparative Example 4

A silica synthetic quartz glass substrate stock as sliced (1220 mm×1400mm×13 mm thick) was lapped and rough-polished, after which it wassubjected to final precision polishing. A soft suede-type polishing padwas used, and a polishing slurry comprising a high-purity colloidalsilica water dispersion resulting from hydrolysis of alkoxysilanes andhaving pH 7 and a SiO₂ concentration of 40% by mass (Fuso Chemical Co.,Ltd., primary particle size 104 nm) was used without addition of sodiumpolyacrylate. Polishing was done under a load of 70.0 gf while thepolishing allowance was an amount sufficient to remove the flawsintroduced in the rough-polishing step (at least about 3 μm).

As a result, the polishing slurry showed a viscosity buildup at thefirst batch from the start of polishing operation so that the polishingoperation became difficult, and the polishing operation becamesubstantially impossible at the second batch.

Defect inspection was carried out as in Example 8. Stains flowing awayfrom the end face were observed, and the number of defects with a sizeof at least 0.3 μm was 84/100 cm² on the average.

Example 15

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a colloidal silica water dispersionhaving a SiO₂ concentration of 40% by mass (Fujimi Inc., primaryparticle size 78 nm) to which 1.0% by mass of aspartic acid (Wako PureChemical Industries Ltd.) was added and diethanolamine was added toadjust to pH 10.0. Polishing was done under a load of 100 gf while thepolishing allowance was an amount sufficient to remove the flawsintroduced in the rough-polishing step (at least about 1 μm).

The polishing was followed by cleaning and drying, after which defectinspection was carried out using a laser conforcal optical systemhigh-sensitivity defect inspector (Lasertec Corp.). The number ofdefects was 4.7 on the average.

Example 16

Defect inspection was done as in Example 15 except that glutamic acid(Wako Pure Chemical Industries Ltd.) was used instead of the asparticacid in Example 15. The number of defects was 4.8 on the average.

Example 17

Defect inspection was done as in Example 15 except that 1.0% by mass ofaspartic acid and 0.5% by mass of benzoic acid were used instead of theaspartic acid in Example 15. The number of defects was 2.2 on theaverage.

Example 18

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 1.0% by mass ofaspartic acid was added (the addition of aspartic acid resulted inpolishing slurry at pH 4.7). Polishing was done under a load of 100 gfwhile the polishing allowance was an amount sufficient to remove theflaws introduced in the rough-polishing step (at least about 1 μm).

Defect inspection was done as in Example 15, finding that the number ofdefects was 7.8 on the average.

Example 19

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7and a SiO₂ concentration of 40% by mass (Fuso Chemical Co.,Ltd., primary particle size 104 nm) to which 1.0% by mass of asparticacid was added and diethanolamine was added to adjust to pH 10.0.Polishing was done under a load of 100 gf while the polishing allowancewas an amount sufficient to remove the flaws introduced in therough-polishing step (at least about 1 μm).

Defect inspection was done as in Example 15, finding that the number ofdefects was 2.9 on the average.

Example 20

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 1.0% by mass ofaspartic acid was added and diethanolamine was added to adjust to pH10.0. Polishing was done under a load of 100 gf while the polishingallowance was an amount sufficient to remove the flaws introduced in therough-polishing step (at least about 1 μm). Polishing was continued justuntil the polishing pad was worn out.

On defect inspection as in Example 15, the number of defects was 1.9 onthe average for those substrates polished in the initial stage and 6.7on the average for those substrates polished in the last stage.

Example 21

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a colloidal silica water dispersionhaving a SiO₂ concentration of 40% by mass (Fujimi Inc., primaryparticle size 78 nm) to which 1.0% by mass of catechol (Wako PureChemical Industries Ltd.) was added and diethanolamine was added toadjust to pH 10.0. Polishing was done under a load of 100 gf while thepolishing allowance was an amount sufficient to remove the flawsintroduced in the rough-polishing step (at least about 1 μm).

The polishing was followed by cleaning and drying, after which defectinspection was carried out using a laser conforcal optical systemhigh-sensitivity defect inspector (Lasertec Corp.). The number ofdefects was 5.1 on the average.

Example 22

Defect inspection was done as in Example 21 except that resorcinol (WakoPure Chemical Industries Ltd.) was used instead of the catechol inExample 21. The number of defects was 5.8 on the average.

Example 23

Defect inspection was done as in Example 21 except that 1.0% by mass ofcatechol and 0.5% by mass of benzoic acid were used instead of thecatechol in Example 21. The number of defects was 3.4 on the average.

Example 24

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 1.0% by mass ofcatechol was added (the addition of catechol resulted in polishingslurry at pH 5.9). Polishing was done under a load of 100 gf while thepolishing allowance was an amount sufficient to remove the flawsintroduced in the rough-polishing step (at least about 1 μm).

Defect inspection was done as in Example 21, finding that the number ofdefects was 7.3 on the average.

Example 25

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 1.0% by mass ofcatechol was added and diethanolamine was added to adjust to pH 10.0.Polishing was done under a load of 100 gf while the polishing allowancewas an amount sufficient to remove the flaws introduced in therough-polishing step (at least about 1 μm).

Defect inspection was done as in Example 21, finding that the number ofdefects was 2.0 on the average.

Example 26

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 1.0% by mass ofcatechol was added and diethanolamine was added to adjust to pH 10.0.Polishing was done under a load of 100 gf while the polishing allowancewas an amount sufficient to remove the flaws introduced in therough-polishing step (at least about 1 μm). Polishing was continued justuntil the polishing pad was worn out.

Defect inspection was done as in Example 21, finding that the number ofdefects was 2.6 on the average for those substrates polished in theinitial stage and 5.2 on the average for those substrates polished inthe last stage.

Example 27

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a colloidal silica water dispersionhaving a SiO₂ concentration of 40% by mass (Fujimi Inc., primaryparticle size 78 nm) to which 0.025% by mass of sodium hyaluronate (WakoPure Chemical Industries Ltd.) was added and diethanolamine was added toadjust to pH 10.0. Polishing was done under a load of 100 gf while thepolishing allowance was an amount sufficient to remove the flawsintroduced in the rough-polishing step (at least about 1 μm).

The polishing was followed by cleaning and drying, after which defectinspection was carried out using a laser conforcal optical systemhigh-sensitivity defect inspector (Lasertec Corp.). The number ofdefects was 4.5 on the average.

Example 28

Defect inspection was done as in Example 27 except that chondroitinsulfate (Wako Pure Chemical Industries Ltd.) was used instead of thesodium hyaluronate in Example 27. The number of defects was 4.8 on theaverage.

Example 29

Defect inspection was done as in Example 27 except that 0.025% by massof sodium hyaluronate and 0.5% by mass of benzoic acid were used insteadof the sodium hyaluronate in Example 27. The number of defects was 3.0on the average.

Example 30

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 0.025% by mass ofsodium hyaluronate (the addition of sodium hyaluronate resulted inpolishing slurry at pH 7.3). Polishing was done under a load of 100 gfwhile the polishing allowance was an amount sufficient to remove theflaws introduced in the rough-polishing step (at least about 1 μm).

Defect inspection was done as in Example 27, finding that the number ofdefects was 4.3 on the average.

Example 31

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 0.025% by mass ofsodium hyaluronate was added and diethanolamine was added to adjust topH 10.0. Polishing was done under a load of 100 gf while the polishingallowance was an amount sufficient to remove the flaws introduced in therough-polishing step (at least about 1 μm).

Defect inspection was done as in Example 27, finding that the number ofdefects was 2.9 on the average.

Example 32

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used and apolishing slurry was used comprising a high-purity colloidal silicawater dispersion resulting from hydrolysis of alkoxysilanes and havingoriginal pH 7 and a SiO₂ concentration of 40% by mass (Fuso ChemicalCo., Ltd., primary particle size 104 nm) to which 0.025% by mass ofsodium hyaluronate was added and diethanolamine was added to adjust topH 10.0. Polishing was done under a load of 100 gf while the polishingallowance was an amount sufficient to remove the flaws introduced in therough-polishing step (at least about 1 μm). Polishing was continued justuntil the polishing pad was worn out.

Defect inspection was done as in Example 27, finding that the number ofdefects was 2.6 on the average for those substrates polished in theinitial stage and 4.7 on the average for those substrates polished inthe last stage.

Comparative Example 5

The procedure was the same as in Example 1 except that no otheradditives were added to the polishing slurry used in the final polishingstep in Example 1. Defect inspection was similarly carried out using alaser conforcal optical system high-sensitivity defect inspector,finding that the number of defects was 52 on the average.

Comparative Example 6

A silica synthetic quartz glass substrate stock as sliced (6 inches) waslapped and rough-polished, after which it was subjected to finalprecision polishing. A soft suede-type polishing pad was used, and apolishing slurry comprising a high-purity colloidal silica waterdispersion resulting from hydrolysis of alkoxysilanes and having pH 7and a SiO₂ concentration of 40% by mass (Fuso Chemical Co., Ltd.,primary particle size 104 nm) was used without addition of otheradditives. Polishing was done under a load of 100 gf while the polishingallowance was an amount sufficient to remove the flaws introduced in therough-polishing step (at least about 1 μm).

As a result, the polishing slurry showed a viscosity buildup at thefourth batch from the start of polishing operation so that the polishingoperation became difficult, and the polishing operation becamesubstantially impossible at the sixth batch.

Defect inspection was carried out as in Example 1, finding that thenumber of defects was 10.9 on the average for those substrates polishedin the initial stage and 265 on the average for those substratespolished in the last stage (sixth batch).

1. A polishing slurry for synthetic quartz glass substrates, comprisinga colloidal solution and a component selected from the group consistingof a carboxylic acid polymer, an acidic amino acid, a phenol, and aglycosaminoglycan, said colloidal solution having a colloidconcentration of 20 to 50% by mass.
 2. The polishing slurry forsynthetic quartz glass substrates of claim 1 wherein the colloidalsolution is a colloidal silica dispersion.
 3. The polishing slurry forsynthetic quartz glass substrates of claim 1 or 2 wherein the carboxylicacid polymer is an acrylic acid polymer.
 4. The polishing slurry forsynthetic quartz glass substrates of claim 1 or 2 wherein the acidicamino acid is aspartic acid or glutamic acid.
 5. The polishing slurryfor synthetic quartz glass substrates of claim 1 or 2 wherein the phenolis catechol, resorcinol or hydroquinone.
 6. The polishing slurry forsynthetic quartz glass substrates of claim 1 or 2 wherein theglycosaminoglycan is hyaluronic acid.
 7. The polishing slurry forsynthetic quartz glass substrates of claim 1, having pH 9 to 10.5. 8.The polishing slurry for synthetic quartz glass substrates of claim 7wherein the pH is adjusted with one or more selected from the groupconsisting of an alkali metal hydroxide, alkaline earth metal hydroxide,basic salt, amine, and ammonia.
 9. The polishing slurry for syntheticquartz glass substrates of claim 1 wherein the synthetic quartz glasssubstrate is a photomask-forming synthetic quartz substrate.